Preparation of organic polymers using organometallic capped monomers to produce metal free polymers

ABSTRACT

A method for the preparation of a variety of engineering polymers and copolymers, in particular aromatic polymers and copolymers which comprises reacting a stannylated reactant containing a first monomeric or polymeric moiety with an electrophilic reactant, usually a di(acid chloride) containing a second monomeric or polymeric moiety. The intermediate and second compound react by way of a condensation reaction to eliminate the tin and polymerise together the first and second moieties. Some novel polymers and copolymers can be prepared using this method.

This application is a division of application Ser. No. 07/355,936, filedMay 23, 1989, now allowed U.S. Pat. No. 4,960,835, which is a divisionof application Ser. No. 07/257,159, filed Oct. 12, 1988, now U.S. Pat.No. 4,845,179, which is a continuation of application Ser. No.07/163,225, filed Feb. 26, 1988, now abandoned, which is a continuationof application Ser. No. 06/900,473, filed Aug. 22, 1986, now abandoned,which is a continuation-in-part of application Ser. No. 06/833,656,filed Feb. 21, 1986, now abandoned, which is a continuation ofapplication Ser. No. 06/704,452, filed Feb. 22, 1985, now abandoned, thedisclosure of which are incorporated herein by reference.

This invention relates to a method of preparing organic polymers andcopolymers.

Condensation polymers and copolymers such as polyesters, polycarbonates,polyamide, polyimides and polyurethanes, which can be used, for example,as engineering thermoplastics, low smoke polymers, or conductivepolymers, are commercially prepared by a variety of methods, many ofwhich require high temperatures and/or potentially hazardous reagents.Studies have been carried out in which certain polymers have beenprepared via specific intermediates. For example Polymer Bulletin 1, pp.383-388 (1979) discloses a method of preparing polyesters using atrimethylsiloxy intermediate, and Canadian Patent No. 786 853 describesa method of preparing a polyimide using a triorganosilyl amineintermediate. However, both of these methods still require relativelyhigh temperatures, for example between 150°-300° C.

Conventional commercial production of block alternating condensationcopolymers is difficult because the copolymerisation temperature isnormally carried out at temperatures above the melting point of thepolymer blocks, in the range of 280° C. 320° C., and therefore they tendto randomise and become random copolymers. Block copolymers are knownwhich do not randomise but only where at least one of the blocks isstable at the copolymerisation temperature. An example is the blockcopolymer `Hytrel` (trade name--from Du Pont) which does not randomisebecause it contains aliphatic polyethers which do not interchange at thereaction temperature.

It has now been discovered, according to the present invention, thatpolymers and copolymers can be synthesised by a more convenient,low-temperature method and that the aforementioned problem ofrandomisation of block copolymers can be alleviated.

Accordingly the present invention provides a method for the preparationof a polymer or copolymer comprising reacting a monomeric, oligomeric orpolymeric nucleophilic reactant of the formula: ##STR1## where E iseither the group (R')_(b) M- or ##STR2## each M is independently anelement selected from Group III, IV or V of the Periodic Table or atransition metal, excluding carbon, silicon, nitrogen, phosphorus, boronaluminium, and titanium;

each R' is independently a substituted or unsubstituted alkyl or arylgroup;

each Y is independently an atom or group selected from oxygen, sulphur,or substituted nitrogen or phosphorus;

each A¹ is independently an aromatic, aliphatic, aromatic/aliphatic,heterocyclic, alicyclic, siloxyl or silane monomeric, oligomeric, orpolymeric moiety;

each a is independently an integer two less than the valence of theelement M to which it pertains;

each b is an integer one less than the valence of the element M to whichit pertains; and

x and y are each independently an integer greater than or equal to 1,

with a substantially stoichiometric amount of an electrophilic reactantselected from the group consisting of

(i) a compound of the formula (V) ##STR3## where each x is independentlyhalide, imidazole, RO-, RS-, or a group capable of reacting with thefirst reactant to eliminate a by-product containing M and X, R being asubstituted or unsubstituted aromatic or aliphatic group or hydrogen;

each B is independently carbon, phosphorus, sulfur, silicon, or a directbond;

each Z is independently oxygen, sulfur, or an imino group; each D isindependent an aromatic, aliphatic, RO-, RS-, or R₂ N- group if B isphosphorus and an aryl, alkyl, or an RO- group if B is silicon;

each d is independently 1 if B is carbon; 0 or 1 if B is phosphorus; 0,1 or 2 if B is sulfur; and 0 if B is silicon or a direct bond;

each e is independently 0 if B is carbon, sulfur, or a direct bond; 1 ifB is phosphorus; and 2 if B is silicon; and A² is an aromatic,aliphatic, aromatic/aliphatic, heterocyclic, alicyclic, siloxyl, orsilane monomeric, oligomeric, or polymeric moiety, which is the same asor different from A¹, or a direct bond;

(ii) a compound of the formula (VI) ##STR4## where X, B, Z, D, d, and eare as hereinbefore defined, provided that B is other than a directbond; and

(iii) combinations of (i) and (ii); to produce a polymer having therepeat unit ##STR5## where A³ is A² or Y-A¹ -Y.

The element M is preferably tin, germanium, lead, or thallium, morepreferably, tin or germanium; especially preferably, tin. One reason forthe desirability of tin is the high cost of germanium compounds comparedto tin. Tetravalent tin is particularly preferred.

The group R' is, for example, a lower alkyl group such as methyl, ethyl,isopropyl, n-propyl, n-butyl, and isobutyl, or an aryl group such asphenyl. Methyl and n-butyl are preferred.

Y is preferably oxygen or NR₂, where R₂ is lower alkyl or hydrogen.

The group A¹ is, for example, substituted or unsubstituted p-phenylene,m-phenylene, 1,4-naphthylene, 2,6-naphthylene, 2,6-pyridinediyl,2,6-pyridinediyl, C-1 through C-6 saturated or unsaturated alkylene, or

    -p-Ph-K-p-Ph-

where p-Ph is p-phenylene and K is a direct bond, O, S, carbonyl,sulfone, or C-1 through C-6 saturated, unsaturated, or fluorinatedalkylene. Preferably, A¹ is p-phenylene, m-phenylene, or -p-Ph-K-p-Ph-,where K is methylene, isopropylidene, or sulfone. A¹ can also beoligomeric or polymeric, for example, a silane or siloxane oligomer orpolymer. Further examples of suitable groups A¹ can be found in therecitation of suitable reagents R"-Y-A¹ -Y-R" (IX), hereinafter.

X is preferably halide, especially chloride or bromide, more especiallychloride. Where X is RO- or RS-, R is preferably lower alkyl, forexample methyl or ethyl, or phenyl.

B is preferably carbon or sulfur, especially carbon.

Z is preferably oxygen.

D is preferably phenyl, lower alkyl, such as methyl or ethyl, or RO- orR₂ N- where R is lower alkyl, for example methyl or ethyl, or hydrogen.

The group A² is, for example, substituted or unsubstituted p-phenylene,m-phenylene, 1,4-naphthylene, 2,6-naphthylene, 2,6-pyridinediyl,2,6-pyridinediyl, C-1 through C-6 saturated, unsaturated, or fluorinatedalkylene, or a direct bond, or

    -p-Ph-K-p-Ph

where p-Ph and K are as hereinbefore defined. Preferably, A² isp-phenylene, m-phenylene, or -p-Ph-K-p-Ph-, where K is methylene,isopropylidene, or sulfone. A² can also be oligomeric or polymeric, forexample, a silane or siloxane oligomer or polymer. Further examples ofsuitable groups A² can be found in the recitation of suitable secondreactants V, hereinafter.

In a preferred embodiment of the invention, E is (R')_(b) M; M istetravalent tin, R' is lower alkyl; Y is oxygen or NR² ; x is 1; x ischloride; B is carbon; and Z is oxygen

In one aspect of the present invention the nucleophilic reactant (I) isof the formula:

    R'.sub.b -M-Y-A.sup.1 -Y-M-R'.sub.b                        (II)

where R', M, Y, A¹ and b are as defined above.

An example of intermediate (II) is a compound having the formula Bu₃ -Sn(4⁺)-O-A¹ -O-Sn(4⁺)-Bu₃

In another aspect of the present invention the nucleophilic reactant (I)is an oligomer of the formula: (III) ##STR6## where Y, A¹, M, R' and bare as defined above; and y is an integer greater than or equal to 2.

An example of nucleophilic reactant (III) is a compound having theformula: ##STR7##

In a further aspect of the present invention the nucleophilic reactant(I) is of the formula: ##STR8## where M, Y, R', b, A' and x are asdefined above; and

M' is a divalent element selected from Group IV of the Periodic Tableexcluding carbon and silicon; preferably divalent tin or lead.

An example of nucleophilic reactant (IV) is a compound having theformula: ##STR9##

Hereinafter the term "nucleophilic reactant" shall be taken to mean anyone of (I), (II), (III) or (IV), unless otherwise specified.

By substituted nitrogen is meant, for example, a substituted orunsubstituted amine or amide group, and by substituted phosphorus ismeant an analogous phosphorus groups.

Examples of nucleophilic reactant (VI) include phosgene, sulphurylchloride, thionyl chloride, and phenyl phosphonic acid dichloride.

Condensation polymers and copolymers can therefore be prepared by theprocess according to the present invention. In many cases thepolymerisation or copolymerisation reaction will be a condensationreaction directly eliminating the by-product, while in other cases theby-product may not be immediately eliminated by the condensationreaction, and can be removed by later processing.

This invention has a number of advantages over known methods forpreparing such polymers and copolymers.

Firstly the process can be carried out at conveniently low temperatures,preferably 0°-150° C., more preferably 40°-80° C., although it is to beunderstood that higher and lower temperatures can also be used. Lowtemperatures are especially advantageous when thermally sensitive groupsare to be incorporated into the polymer or copolymer. For examplecarbon-carbon double and triple bonds can be incorporated withoutcross-linking occurring, nitrogen-nitrogen bonds can be included withoutthe risk of nitrogen evolution, as can halogenoethylyl groups withoutthe risk of dehydrochlorination, and carbodiimide groups can beincorporated. Also, by using the method according to the presentinvention, it is possible to prepare, for example, copolymers whereinone type of polymer block is thermally sensitive, and copolymers whereinthe different types of polymer block each contain different thermallysensitive groups.

The reagents used in the process can be chosen to be relativelynon-hazardous, for example by using n-butyl tin(4+) derivatives.

Another advantage is that the by-product of the process is soluble inmany solvents, making purification of the polymeric product an unusuallyeasy task Furthermore the by-product can be readily converted back tothe starting reagent.

The present invention is especially advantageous in that it provides auseful method for the preparation of copolymers, especially condensationcopolymers. By copolymer is meant a polymer containing two or moredifferent repeating units. These different repeating units may be fromthe same family, for example both esters, to give a copolyester, or theymay be from different families, for example an ester and an amide togive a copolyesteramide. Three or more different monomers may becopolymerised to make terpolymers, which will hereinafter be includedwithin the term "copolymer". Condensation copolymers are copolymerswherein one or more of the polymer blocks is a condensation polymer.

Random, alternating and block copolymers can all be prepared by theprocess according to the present invention, but the preparation ofcontrolled block copolymers is especially useful as such polymers areoften difficult to prepare using known commercial methods, as statedabove.

By block copolymer is meant a compound containing at least two differentblocks, at least one of these blocks being polymeric. Usually all theblocks incorporated in the copolymer are polymeric and hereinafter eachcompound block shall be referred to as a polymer block although it is tobe understood that blocks comprising a single unit are also included.

Many different types of copolymer can be prepared by the processaccording to the present invention. For example, multi-block copolymers,of the type ABABA . . . or containing more than two different blocks,may be prepared A-B di-block copolymers can also be prepared, thesebeing useful in the blending of polymers of the type A and type B.

Random copolymers may be obtained by mixing the different monomerstogether before any substantial polymerisation has taken place.Alternating copolymers may be obtained by allowing complete reaction of,for example, two monomers before the addition of another monomer,followed by polymerisation to high molecular weight

The number average molecular weight of a polymer or copolymer obtainedby the process according to this invention is preferably at least10,000, more preferably at least 30,000, expressed as number averagemolecular weight in polystyrene equivalents measured by GPC or ofReduced Viscosity at least 0.25 preferably greater than 0.7 for a 1%solution at 25° C. Usually higher molecular weights are needed tooptimise properties in the case of those polymers of an aliphatic naturethan for those with a largely aromatic nature.

The solvent used for the process is chosen such that the desiredmolecular weight of the chosen polymer is reached Altering thestructural form may necessitate a change of solvent, for example, therandom copolymer of any given set of specific monomers may havedifferent solubility parameters from the alternating isomer, the randomor less ordered copolymer usually being more soluble in any specificsolvent than an alternating or more ordered copolymer. The solvent orspecific mixtures of solvents chosen can be used as a method ofmolecular weight control, especially when blocks of particular molecularweight are needed. Many solvents dissolve the by-product leaving arelatively clean polymer which can be cleaned further by solventextraction. Typical reaction solvents include For example, chloroform,xylene, toluene, tetrahydrofuran, chlorobenzene, 1,2-dichloroethane anddimethylformamide. Complex reaction solvents can also be used, such aslithium chloride/dimethelacetamide.

If desired the process may include the use of one or more catalysts toenhance the reaction rate. Catalysts suitable for the process can bereadily determined experimentally by a person skilled in the relevantfield, an example being N,N-dimethylamino-pyridine.

As will be readily apparent to one skilled in the field of polymersynthesis, by appropriate selection of nucleophilic and electrophilicreactants, polymers or polymer blocks, for example esters, carbonates,thioesters, thiocarbonates, amides, thioamides, imides, thioimides,urethanes, fluoroaromatics, fluoroaliphatics and sulphonylimides can beprepared by the process of the invention. Copolymers can be similarlyprepared by combining two or more of the above polymer blocks by theprocess according to the present invention, for examplecopolyesteramides and terpolyesteramideurethanes. It is to be understoodthat oligomers are included within the term `polymer`.

The nucleophilic reactant can be obtained by a number of differentmethods. The nucleophilic reactant having the formula (II) may beprepared, for example, from

(i) a reagent having the formula

    R'.sub.b -M-O-M-R'.sub.b                                   (VII)

where R', M and b are as defined above,

an example of reagent (VII) being:

    Bu.sub.3 -Sn(4.sup.+)-O-Sn(4.sup.+)-Bu.sup.3 ;

or (ii) a reagent having the formula

    R'.sub.b -M-X                                              (VIII)

where R', M and b are as defined above; and

X is halide, -OR, or -NR₂,

where R is a substituted or unsubstituted alkyl or aryl group or ahydrogen atom

an example of reagent (VIII) being Bu₃ -Sn(4⁺)-OMe; and reacting eitherreagent, in substantially stoichiometric proportions, with either (a) acompound having the formula:

    R"-Y-A.sup.1 -Y-R"                                         (IX)

where Y and A' are as defined above; and

each R" is independently an atom selected from hydrogen, sodium,potassium or cesium, or an acetate group;

examples of reagent (IX) being H-O-Al-O-H and H₂ -A'-NH₂ ;

or (b) reacting reagent (VII) with a compound containing a carbonyl,thiocarbonyl, isocyanate, isothio-cyanate or nitrile group. Where acarbonyl group is used these must be activated by anelectron-with-drawing group such as CF₃, CCl₃, trinitrophenyl orsulphonylphenyl; examples of such compounds include: ##STR10## where Aris an aryl group;

or (c) reacting reagent (VIII), where X is not a halide, with adiisocyanate, dinitrile, diisothiocyanate or dicarbonyl

The nucleophilic reactant having the formula (III) may be prepared, forexample, from a reagent of the formula:

    R'.sub.b -M-X.sub.g                                        ((XI)

where R', M and b are as defined above,

X is selected from oxygen, halide, -OR, or -NR₂, where R is substitutedor unsubstituted alkyl or aryl group or a hydrogen atom;

g is 1 when X is oxygen or 2 when X is not oxygen; and reacting reagent(XI) with compound (IX) above. Examples of reagent (XI) include Bu₂-Sn(4⁺)-(OMe)₂ and Bu₂ -Sn(4⁺)-O.

The nucleophilic reactant having the formula (IV) may be prepared, forexample by reacting astannocene, ##STR11## containing a sufficientamount of compound (VII) or (VIII) to act as capping agents, withcompound (IX) above

Preferably the nucleophilic reactant is obtained from the reactionbetween compounds (VII) or (VIII) and (IX) or between compounds (VII)and the carbonyl compound, ##STR12##

The solvent used in the preparation of the nucleophilic reactant varieswith the type of reagent used. Where the by-product of the reaction isvolatile, then a solvent capable of removing the by-product bydistillation is preferred For example, if the by-product is water thensolvents such as xylene or chlorobenzene may be used. Where theby-product is a salt then xylene, toluene or some other inert solvent issuitable, enabling the by-product to be removed by filtration forexample. It is preferred that the solvent should boil at the desiredreaction temperature as this affords a simple method of temperaturecontrol by reflux.

Once the polymer or copolymer has been isolated it is possible for theby-product to be easily removed, for example by extraction with acetone,hexane, methanol or other simple solvents which do not affect thepolymer adversely. The by-product can then be converted back to itsoriginal form by reaction with suitable, well-known reagents or it canbe recovered by distillation.

Capping agents may be employed and are added to the polymerisationreaction mixture to cap the polymer or copolymer on at least one end ofthe chain. This terminates continued growth of that chain and may beused as a method of controlling the resulting molecular weight of thepolymer or copolymer. Such capping agents may be added at the start ofthe reaction or at any time during the reaction or when it is decided toterminate the reaction. The capping agent used depends on the end to beterminated. After the polymerisation according to the present inventionthe polymer or copolymer chain contains substantially two different endgroups, that is either the group (R')_(b) M- or the group -X. To cap thegroup (R')_(b) M- a capping agent such as a monofunctional acid chloridecan be used, and for the group -X a capping agent such as amonofunctional tin derivative of the formula A3-OSnBu3, where A3 can beany of the moieties mentioned for A'but is monofunctional, can be used.

In the nucleophilic reactant the R' group may be, for example, anunsubstituted alkyl group (e.g. methyl, ethyl, propyl, isopropyl, butyl,pentyl, octyl etc ), a substituted alkyl group e.g. benzyl, phenylethyl,etc.) or a substituted or unsubstituted aryl group (e.g. phenyl,napthyl, biphenyl, etc.), or an alicylic group. Preferably R' is analkyl group containing 3 or 4 carbon atoms, more preferably a butylgroup, and especially an n-butyl group. The number of R' groups attachedto the element M depends upon the valency of M. For example, in theintermediate of formula (II) if M is tin(4+), then b (the number of R'groups) is 3.

Where M is a transition metal, it may be any one element selected fromscandium, vanadium, chromium, manganese, iron, cobalt, nickel, copper,zinc, yttrium, zirconium, niobium, molybdenum, technetium, rubidium,ruthenium, palladium, silver, cadmium, lanthanum, hafnium, tantalum,tungsten, rhenium, osmium, iridium, platinum, gold or mercury. For anygiven reaction, the actual transition metal chosen will depend upon itscost, availability and suitability for use in the reaction which can bedetermined by ordinary trial and error.

There are many groups suitable for use as the A1 and A2 moieties in thenucleophilic reactant and the electrophilic reactant (V) respectively.As stated above these moieties are selected from an aromatic, aliphatic,aromatic/aliphatic, hetero-cyclic, alicylic, siloxyl or silanebifunctional moiety. This includes substituted or unsubstitutedmoieties, heteroaromatic, heteroaliphatic and multiple aromatic moietieswhich may be joined by an oxygen or sulphur atom or a sulphone, imide orketone group for example, moieties which are solely silicon based andcontain no back-bone carbon atoms as in the case of silycic acidchlorides, or siloxane or silane chains with carbon containing moietiesjoined directly to silicon as chain end groups In addition the A2 moietymay contain an appropriate atom, for example oxygen or sulphur, which isbendable with the B atom in the second compound (V). An example of sucha moiety is that obtained from chloroformate.

It will be understood that reference to aromatic oligomeric or polymericmoieties mean moieties which have arylene units incorporated in therepeating unit of their backbone chain, not merely appended as sidegroups to the chain as for example in the case of polystyrene.Preferably these aromatic moieties will be wholly aromatic. By whollyaromatic is meant that the backbone chain of the moiety contains no twoadjacent aliphatic carbon atoms. References to aromatic oligomers orpolymers are to be construed accordingly.

Some examples of reagents (IX) incorporating suitable A¹ moieties are asfollows:

hydroquinone;

resorsinol;

catechol;

chlorohydroquinone;

bromohydroquinone;

nitrohydroquinone;

methylhydroquinone;

phenylhydroquinone;

vinylhydroquinone;

allylhydroquinone;

alkoxyhydroquinone;

aryloxyhydroquinone;

acetylhydroquinone;

benzoylhydroquinone;

benzylhydroquinone;

tetrafluorohydroquinone;

dihydroxypyridine;

2,4-dihydroxy-5,6-dimethylpyrimidine;

4,6-dihydroxy-2-methylpyrimidine;

4,6-dihydroxy-2-methylmercapto-pyrimidine;

3,6-dihydroxypyridazine;

2,3-dihydroxyquinoxaline;

4,8-dihydroxyquinoline;

4,6-dihydroxypyrimidine;

3,5-dihydroxy-2-nitropyridine;

4-(p-nitrophenylazo) resorcinol;

4-hydroxylbenzylalcohol

p-xylene α, α'-diol

1,1-bis(4-hydroxyphenyl)-1-phenyl)ethane;

1,1-bis(4-hydroxyphenyl)-1,1-diphenyl methane;

1,1-bis(4-hydroxyphenyl)cyclooctane;

1,1-bis(4-hydroxyphenyl)cycloheptane;

1,1-bis(4-hydroxyphenyl)cyclohexane;

1,1-bis(4-hydroxyphenyl)cyclopentane;

2,2-bis(3-propyl-4-hydroxyphenyl)decane;

2,2-bis(3,5-dibromo-4-hydroxyphenyl)nonane;

2,2-bis(3,5-isopropyl-4-hydroxyphenyl)nonane;

2,2-bis(3-ethyl-4-hydroxyphenyl)octane;

4,4-bis(hydroxyphenyl)heptane;

3,3-bis(3-methyl-4-hydroxyphenyl)hexane;

3,3-bis(3,5-dibromo-4-hydroxyphenyl)hexane;

2,2-bis(3,5-difluoro-4-hydroxyphenyl)butane;

2,2-bis(4-hydroxyphenyl)propane (Bisphenol A)

1,1-bis(3-methyl-4-hydroxyphenyl)ethane;

1,1-bis(4-hydroxyphenyl)methane;

2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane;

bis(3,5-diisopropyl-4-hydroxyphenyl)sulphoxide;

bis(3-methyl-5-ethyl-4-hydroxyphenyl)sulphoxide;

bis(3,5-dibromo-4-hydroxyphenyl)sulphoxide;

bis(3,5-dimethyl-4-hydroxyphenyl)sulphoxide;

bis(3-methyl-4-hydroxyphenyl)sulphoxide;

bis(4-hydroxyphenyl)sulphoxide;

bis(3,5-dichloro-4-hydroxyphenyl)sulphoxide;

bis(3,5-diisopropyl-4-hydroxyphenyl)sulphone;

bis(3,5-methyl-5-ethyl-4-hydroxyphenyl)sulphone;

bis(3-chloro-4-hydroxyphenyl)sulphone;

bis(3,5-dibromo-4-hydroxyphenyl)sulphone;

bis(3,5-dimethyl-4-hydroxyphenyl)sulphone;

bis(3-methyl-4-hydroxyphenyl)sulphone;

bis(4-hydroxyphenyl)sulphone;

bis(3,5-dichloro-4-hydroxyphenyl)sulphone;

2,6-dihydroxynaphthalene;

1,7-dihydroxynaphthalene;

1,6-dihydroxy-4-methylnaphthalene;

3,3',5,5'-tetrabromo-4,4'-dihydroxybiphenyl;

3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl;

3,3'-dichloro-4,4'-dihydroxybiphenyl;

3,3'-diethyl-4,4'-dihydroxybiphenyl;

3,3'-dimethyl-4,4'-dihydroxybiphenyl;

4,4'-dihydroxybiphenyl;

bis(3-chloro-5-methyl-4-hydroxyphenyl)ether;

bis(3,5-dibromo-4-hydroxyphenyl)ether;

bis(3,5-dichloro-4-hydroxyphenyl)ether;

bis(3-ethyl-4-hydroxyphenyl)ether;

bis(3-methyl-4-hydroxyphenyl)ether;

bis(4-hydroxyphenyl)ether;

dihydroxyazobenzene;

4,4'-dihydroxybenzalazine;

dihydroxybenzophenone;

3-methyl-4,4'-dihydroxybenzophenone;

3,3'-dimethyl-4,4'-dihydroxybenzophenone;

3,3'-dichloro-4,4'-dihydroxybenzophenone;

4,4'-dihydroxybenzophenone;

2,4,4'-trihydroxybenzophenone;

2,2',4,4'-tetrahydroxybenzophenone;

hydroxybenzyl alcohol;

α, ω-dihydroxypolyphenylene ether ketones; ##STR13## α,ω-dihydroxypolyalkylene ether ketones (alkyleneis C1 to C6)4,4'-dihydroxystilbene;

3,3'-dichloro-4,4'-dihydroxystilbene;

3,3'-dimethyl-4,4'-dihydroxystilbene;

3,3',5,5'-tetramethyl-4,4'-dihydroxystilbene;

3,5-dihydroxystilbene;

α, ω-dihydroxypolyphenylene ether sulphones;

α, ω-dihydroxypolyalkylene ether sulphones; (alkylene is C1 to C6);

1,2-dihydroxyethane;

1,3-dihydroxypropane;

1,2-dihydroxypropane;

1,4-dihydroxybutane;

1,4-dihydroxybut-2ene;

dihydroxycyclohexanes;

1,4-dihydroxy-2-chlorobutane;

triethylene glycol;

α, ω-dihydroxypolytetrahydrofuran;

e.g. TeracolR 600, 1000 or 2000 from Du Pont;

α, ω-dihydroxy polysiloxane;

α, ω-bis(4-hydroxyphenyl)polysiloxane;

dihydroxystyrene;

1,2-dihydroxyacenaphthene;

dihydroxyacridine;

dihydroxyanthracene;

1,1'-dihydroxy-2,2'-binaphthyl, and isomers;

dihyroxycarbazole;

dihydroxychrysene;

dihydroxybibenzofuran;

dihydroxy-1,7-dimethylphenanthrene;

dihydroxy-2,3-dinitronaphthalene;

dihydroxydiphenylsulphide;

3,3'-dihydroxyleprotene;

dihyroxynitroazobenzene;

dihydroxyperylene;

dihydroxyphenazine;

dihydroxypyrene;

dihydroxy-1,2,3,4-tetrahydroanthracene;

dihydroxy-3',4',5,7-tetramethoxyflavone;

dihydroxy-5-undecyclbenzene;

5,7 dihydroxycoumarin;

6,7 dihydroxycoumarin;

α, ω-dihydroxypolyesters; ##STR14## α, ω-dihydroxypolyamides; α,ω-dihydroxypolycarbonates

α, ω-dihydroxypolyurethanes;

4,4'-biphenyldithiol;

4,4'-biphenyletherdithiol;

2,2'-bis(4-phenylenethiol)propane;

4-mercapto-1-anthracenol;

3,4-toluenedithiol;

1,4-phenylenedithiol;

1,6-hexanedithiol;

4-hydroxythiophenol;

N,N'-Diacetyl-1,4-diaminobenzene;

4,4'-diaminobiphenyl;

1,4-diaminobenzene;

1,3-diaminobenzene;

4,4'-diaminodiphenylether;

4,4'-diaminodiphenylsulphone;

Examples of the electrophilic reactant (V) incorporating the A2 moietyare as follows:

1,4-benzene-dicarboxylic acid dichloride;

1,3-benzene-dicarboxylic acid dichloride;

1,2-benzene-dicarboxylic acid dichloride;

mono-, di-, tri- and tetra- alkyl substituted benzene dicarboxylic aciddichlorides;

mono-,di-, tri- and tetra- aryl substituted benzene dicarboxylic aciddichlorides;

mono-, di-, tri- and tetra halogenated benzene dicarboxylic aciddichlorides;

mono-, and di- nitro substituted benzene dicarboxylic acid dichlorides;

5-nitro-1,3-benzene dicarboxylic acid dichloride;

5-maleimido-1,3-benzene dicarboxylic acid dichloride;

pyridine dicarboxylic acid dichloride;

5-methyl-1,3-benzene dicarboxylic acid dichloride;

diphenylether dicarboxylic acid dichloride;

5-phenyl-1,3-benzene dicarboxylic acid dichloride;

naphthalene dicarboxylic acid dichloride;

stilbene dicarboxylic acid dichloride;

azobenzene dicarboxylic acid dichloride;

benzophenone dicarboxylic acid dichloride;

diphenyl sulphone dicarboxylic acid dichloride;

biphenyl dicarboxylic acid dichloride;

tetrafluoro-1,4-benzene dicarboxylic acid dichloride;

anthracene dicarboxylic acid dichloride;

4,4'-isopropylidene di(benzoyl chloride);

oxalic acid dichloride;

1,4-bis(chloroformyl)benzene quinoline dicarboxylic acid dichloride;

polyester -α, ω-dicarboxylic acid dichloride;

polyaryletherketone-α, ω-dicarboxylic acid dichloride;

polyarylethersulphone-α, ω-dicarboxylic acid dichloride;

polyarylethersulphone-α, ω-disulphonic acid dichloride;

polyamide-α, ω-dicarboxylic acid dichloride;

polycarbonate dicarboxylic acid dichloride;

cyclohexane dicarboxylic acid dichloride;

adipic acid dichloride;

1,2 ethylene dicarboxylic acid dichloride;

malonic acid dichloride;

succinic acid dichloride;

chlorosuccinic acid dichloride;

maleic acid dichloride;

dibromomaleic acid dichloride;

diethylmaleic acid dichloride;

fumaric acid dichloride;

glutaric acid dichloride;

hexafluoroglutaric acid dichloride and other fluorinatedaliphatic/aromatic carboxylic acid dichlorides;

itaconic acid dichloride;

mesaconic dichloride;

muconic dichloride;

cis-5-norbornene-endo-2,3-di(carboxylic acid dichloride);

phenylene di(acetic acid) dichloride;

sebacic acid dichloride;

tetrahydrofuran dicarboxylic acid dichloride;

undecane dicarboxylic acid dichloride;

2,2'-bis(4-chloroformylphenyl)propane;

phenyl phosphonic acid dichloride;

diphenylether disulphonic acid dichlorde.

polycarbonate-α, ω-bischloroformate;

oxaloyl chloride

dichlorodimethylsilane;

dichlorodiphenylsilane;

dichloromethylphenylsilane;

dichlorotetramethyldisiloxane;

α, ωdichloro polydimethylsiloxane;

α, ωdichloro polymethylphenylsiloxane;

dichloracetylene;

1,4-dichlorobutadiene;

α, ω-dichloropolyphosphazene;

polydiorganosiloxane-α, ω-(p-phenylenedicarboxylic acid dichloride).

Thus, for example, a polyester is prepared by reacting a diol of formulaIX with a reagent of formula VII or VIII to form a nucleophilic reactantI. This nucleophilic reactant is then polymerized with an electrophlicreactant V to yield a polyester. By way of specific illustration, thediol hydroquinone is reacted with either bis-tri-n-butyltin oxide ortri-n-butyltin methoxide to form a nucleophilic reactant of thestructure

    Bu.sub.3 Sn-O-p-Ph-O-SnBu.sub.3.

This is then reacted with terephthaloyl chloride as an electrophilicreactant, to produce the polyester having the repeat unit

    [-O-p-Ph-O-CO-p-Ph-CO-].

Analogously, a polyamide is prepared by reacting a diamine of formula IXwith a reagent of formula VII or VIII to form a nucleophilic reactant I.This first reactant is then polymerized with an electrophilic reactant Vto yield a polyamide. By way of specific illustration, the diaminep-phenylenediamine is reacted with either bis-tri-n-butyltin oxide ortri-n-butyltin methoxide to form a nucleophilic reactant of thestructure

    Bu.sub.3 Sn-NH-p-Ph-NH-SnBu.sub.3.

This is then reacted with isophthaloyl chloride as the electrophilicreactant to produce the polyamide having the repeat unit

    -NH-p-Ph-NH-CO-m-Ph-CO-

where m-Ph is m-phenylene.

Random copolymers can be prepared by using more than a single compoundIX to form the nucleophilic reactant I, or by using more than a singleelectrophilic reactant V, or both. By way of specific illustration, inthe preparation of the polyamide set forth immediately above, a randomcopolyamide is produced if, instead of using only p-phenylenediamine, amixture of m- and p-phenylenediamines is used. Alternatively, a mixtureof iso- and terephthaloyl chlorides can be used.

It is to be recognized that the degree of randomness can be affected bythe relative reactivities of the comonomers and the sequence and timingof their addition These parameters can be utilized to increase ordecrease the degree of randomness, as desired. For example, if a mixtureof nucleophilic reactants in which one comonomer is more reactive isused, it may react substantially before the other one, leading to a more"blocky" copolymer.

Block copolymers are prepared according to the method of this inventionby reacting a precursor polymer

    H-Y-P-Y-H                                                  (XII)

with a reagent VII or VIII to produce a first polymer block

    (R').sub.b M-Y-P-Y-M(R').sub.b                             (XIII).

This first polymer block is then reacted with a second polymer block ofthe formula ##STR15## to produce a block copolymer having the repeatingblocks of the formula ##STR16##

In formula XIII, R', b, M, and Y are as hereinbefore defined. H ishydrogen. P is a divalent polyolefin, polyester, polyamide,polyphenylene ether ketone, polyalkylene ether ketone,polytetrahydrofurane, polydimethylsiloxane, polymethylphenylsiloxane,polyphenylene ether sulfone, polyalkylene ether sulfone, polycarbonate,or polyurethane polymeric group. Further examples of suitable groups Pcan be found in the following illustrative but not exclusive list ofsuitable precursor polymers H-Y-P-Y-H:

α, ω-dihydroxypolyphenylene ether ketones; ##STR17## α,ω-dihydroxypolyalkylene ether ketones (alkylene is C₁ to C₆ ;

α, ω-dihydroxypolytetrahydrofuran; e.g. Teracol® 600, 1000 or 2000 fromDu Pont;

α, ω-dihydroxy polysiloxane;

α, ω-bis(4-hydroxyphenyl)polysiloxane;

α, ω-dihydroxypolyphenylene ether sulphones;

α, ω-dihydroxypolyalkylene ether sulphones; (alkylene is C₁ to C₆);

α, ω-dihydroxypolyesters; ##STR18## α, ω-dihydroxypolyamides; α,ω-dihydroxypolycarbonates; and

α, ω-dihydroxypolyurethanes;

In formula XIV, X, Z, d, B, D, and e are as hereinbefore defined. Q is adivalent polyester, polyamide, polyphenylene ether ketone, polyphenyleneether sulfone, polycarbonate, polydimethylsiloxane, orpolymethylhenyl-siloxane polymeric group. Further examples of suitablegroups Q can be found in the following illustrative but not exclusivelist of suitable second polymer blocks XIV:

polyester-α, ω-dicarboxylic acid dichloride;

polyaryletherketone-α, ω-dicarboxylic acid dichloride;

polyarylethersulphone-α, ω-dicarboxylic acid dichloride;

polyarylethersulphone-α, ω-disulphonic acid dichloride;

polyamide-α, ω-dicarboxylic acid dichloride;

polycarbonate-α, ω-dicarboxylic acid dichloride;

α, ω-dichloro polydimethylsiloxane;

α, ω-dichloro polymethylphenylsiloxane;

α, ω-dichloropolyphosphazene; and

polydiorganosiloxane-α, ω-(p-phenylene dicarboxylic acid dichloride).

By way of specific illustration of the preparation of a block copolymer,the first polymer block

    Bu.sub.3 Sn-O-(p-Ph-CO-p-Ph-O)n-SnBu.sub.3

where n is an integer greater than 1, is block copolymerized with thesecond polymer block

    C1-(SiMe.sub.2 -O-)m-SiMe.sub.2 -C1

where m is an integer greater than 1, to produce a block copolymerhaving the repeating blocks

    [-O-(p-Ph-CO-p-Ph-O).sub.n -(SiMe.sub.2 -O-).sub.m -SiMe.sub.2 -].

In a preferred embodiment of the invention, the first polymer block XIIIis prepared by reacting a stoichiometric excess of a nucleophilicreactant

    (R').sub.b M-Y-A.sub.1 -Y-M(R').sub.b

where R', b, M, Y, and A¹ are as hereinbefore defined, with anelectrophilic reactant (i), (ii), or (iii), as hereinbefore defined. Inanother preferred embodiment of the invention, the second polymer blockis prepared by reacting the nucleophilic reactant with a stoichiometricexcess of the electrophilic reactant (i), (ii), or (iii). In yet anotherpreferred embodiment of the invention, both the first and second polymerblocks are prepared as mentioned immediately above. In summary, using anexcess of the nucleophilic reactant produces a first polymer block XIII,while using an excess of the electrophilic reactant produces a secondpolymer block XIV.

In a particularly advantageous embodiment, each of the blocks XIII andXIV is prepared by the above-described stoichiometric imbalance method,then the blocks are mixed and block copolymerized without the priorisolation each block. In such an embodiment, the solvent used for thepreparation of each of blocks XIII and XIV can be the same or different.

Those skilled in the art will appreciate that the size of the first andsecond polymer blocks can be controlled by varying the degree ofstoichiometric imbalance.

By way of specific illustration, a first block

    Bu.sub.3 Sn-(OCH.sub.2 CH.sub.2 O-CO-p-Ph-CO).sub.n -OCH.sub.2 CH.sub.2 O-SnBu.sub.3

where n is an integer greater than 1, can be prepared from ethyleneglycol and terephthaloyl chloride, using an excess of the former. Asecond block

    C1-CO-m-Ph-CO-(O-p-Ph-0-CO-m-Ph-CO)m-C1

where m is an integer greater than 1, can be prepared from hydroquinoneand isophthaloyl chloride, using an excess of the latter. These twoblocks can be block copolymerized to produce the block copolyesterhaving the repeating blocks

    [-(OCH.sub.2 CH.sub.2 O-CO-p-Ph-CO).sub.n -]

and

    [-CO-(O-p-Ph-0-CO-m-Ph-CO).sub.m-].

It will also be evident to those skilled in the art that if one of theend groups (R')_(b) M- in the first polymer block XIII and one of theend groups ##STR19## in the second block XIV are replaced by inertgroups F and F', respectively, then a diblock copolymer having theformula ##STR20## is produced. If only the first polymer block XIII hasan end group replaced by an inert group F, a block copolymer with theformula ##STR21## is produced, and vice-versa.

In addition to the new polymers and copolymers specifically described,some new classes of copolymers have been discovered.

A first class is a block copolymer comprising at least onenon-ethylenically unsaturated aromatic polymer block and at least oneethylenically unsaturated polymer block.

A second class of block copolymers is a block copolymer containing atleast one wholly aromatic polymer block of the formula: ##STR22## whereY,B,Z,D,B,d and e are as defined above; Ar¹ and Ar² are eachindependently a monomeric, oligomeric or polymeric aromatic moiety whichat least bifunctional;

p is an integer greater than 1.

Preferably the polymer block (XII) is a polyester, and more preferablycontains a bisphenol residue A number of different polymer blocks can becopolymerised with the polymer block (XII).

An example of a copolymer comprising a polyester block and anethylenically unsaturated block is a copolymer of the formula: ##STR23##where each R¹ is independently a substituted or unsubstituted aromaticor aliphatic group which is at least bifunctional, and is preferably amethylene or substituted or unsubstituted phenylene group.

q and n are each independently an integer greater than or equal to 1;and

p is an integer greater than 1.

An amide block can also be copolymerised with the polymer block (XII).An example is a copolyesteramide of the formula: ##STR24## where R,p,qand n are as defined above and each R' is independently a substituted orunsubstituted alkyl or aryl group or a hydrogen atom, and is preferablya substituted or unsubstituted phenylene group.

Another type of block copolymer containing a polymer block of formula(XII) is one comprising a polyester block and a polyether-containingblock. For example: ##STR25## where p, q and n are as defined above; xis an integer greater than 1; and

y is an integer greater than or equal to 1.

Specific details of the invention are illustrated by the followingexamples. All solvents and materials mentioned in the examples aredegassed, especially to exclude carbon dioxide, prior to their use.

EXAMPLE 1

This example describes the preparation of a copolyester having therepeat unit ##STR26##

A mixture of 97.82 grams (0.43 mol) 2,2'-bis(4-hydroxyphenyl)propane,255.41 grams (0.43 mol) of bis-(tri-n-butyl tin) oxide and 500 ml ofxylene were heated under reflux in a nitrogen atmosphere for 4 hours. ADean-Stark trap was used to remove the water formed during the reaction.Thereafter 300 ml of the xylene was removed at atmospheric pressure andthe remaining 200 ml at reduced pressure (20 mm/Hg). After allowing theremaining liquid to cool to room temperature 150 ml of dry chloroformwas added to the liquid. To this solution was then added 43.76 grams(0.215 mol) isophthalyoyl dichloride in 100 ml of dry chloroform. Aftera period of not less than 20 minutes 43.76 grams (0.215 mol) ofterephthaloyl dichloride in 100 ml of chloroform was added Reflux (70°C.) was maintained for 20 hours. The viscous cloudy solution was pouredinto two liters of methanol in a Waring blender and the precipitatecollected by filtration Residual n-butyl tin chloride was removed bycontinuous extraction for sixteen hours with methanol.

¹³ C n.m.r., infra-red, and 'H n.m.r. spectra were consistent with theexpected structure and matched those of the commercial polymer "Arylef"(trade name--from Solvay), which is a random copolymer of the samemonomers. The Reduced Viscosities (RV) of the polymer of the example andof "Arylef", and the molecular weights by GPC and expressed inPolystyrene equivalents were similar. The Dynamic Mechanical Analysiswas also similar although not precisely the same. Some results andcomparisons are shown in Table 1.

                  TABLE 1                                                         ______________________________________                                                    Experimental                                                                  Sample   Arylef                                                   ______________________________________                                        Mn*           31,3000    30,400                                               Tg            185° C.                                                                           188° C.                                       Ts**          238° C.                                                                           241° C.                                       RV***         0.73       0.72                                                 ______________________________________                                         *G.P.C. in chloroform solution, polystyrene equivalents.                      **Softening point                                                             ***1% solution in chloroform                                             

A similar result is obtained if the entire reaction is carried out inchlorobenzene.

EXAMPLE 2

Preparation of the polyester ##STR27##

A mixture of 20.05 grams (0.08 mol) bis(4-hydroxy-phenyl)sulphone, 47.75grams (0.08 mol) of bis-(tri-n-butyl tin) oxide and 500 ml of xylenewere heated under reflux in a nitrogen atmosphere for 3 hours. ADean-Stark trap was used to remove the water formed during the reaction.Thereafter 300 ml of the xylene was removed at atmosphoric pressure andthe remaining 200 ml at reduced pressure (20 mm/Hg). After allowing theremaining liquid to cool to room temperature, when it may crystallizeunder certain conditions, 50 ml of dry chloroform was added to theremaining liquid. To this solution was added 8.13 grams (0.04 mol)isophthalol dichloride in 50 ml of dry chloroform. After a period of notless than twenty minutes 8.13 grams (0.04 mol) of terephthaloyldichloride in 50 ml of dry chloroform was added. Reflux (70° C.) wasmaintained for 20 hours. The viscous cloudy solution was poured into oneliter of methanol and the precipitate collected by filtration. Residualtri-n-butyl tin chloride was removed be extraction with methanol for 8hours.

The structure of the resulting polysulphone ester was confirmed by ¹³ Cn.m.r. spectroscopy and infra-red spectrophotometry.

The polymer had a reduced viscosity of 0.37 dl/g (1% solution inchloroform).

EXAMPLE 3

Preparation of the polycarbonate ##STR28##

A mixture of 100.32 grams (0.44 mol) of 2,2'-bis (4-hydroxyphenyl)propane, 282.54 grams (0.88 mol) of tributyltin methoxide and 700ml of chlorobenzene were heated under reflux. Methanol was removed asthe by-product using a fractionating column. Upon completion thesolution of stannylated bisphenol was allowed to cool to roomtemperature. After cooling, 43.47 grams (0.44 mol) of phosgene gas wasslowly passed into the solution. After the addition was complete thesolution was stirred at room temperature for 2 hours and then at 70° C.for 10 hours. The viscous solution was poured into 2 liters of methanolin a Waring blender. The precipitate was collected by filtration.Residual tri-n-butyl tin chloride was removed by continuous extractionfor 16 hours with methanol.

The structure of the resulting "Bisphenol A" polycarbonate ("BisphenolA" is a trade name) was confirmed by ¹³ C n.m.r. spectroscopy andinfra-red spectrophotometry.

The polymer had a reduced viscosity of 0.72 dl/g. (1% solution inchloroform).

EXAMPLE 4

Preparation of the polycarbonate ##STR29##

A mixture of 26.27 grams (0.115 mol) 2,2'-bis(4-hydroxyphenyl)propane,68.60 grams (0.115 mol) bis-tri-n-butyl tin) oxide and 600 ml of xylenewere heated under reflux in a nitrogen atmosphere for 4 hours. A DeanStark trap was used to remove the water formed during the reaction.Thereafter 350 ml of xylene was removed at atomspheric pressure and theremaining 250 ml under reduced pressure (20 mm/Hg). After allowing theremaining liquid to cool to room temperature 50 ml of dry chloroform wasadded. To this solution was added 40.65 grams (0.115 mol)2,2'-bis(4-chloroformylphenyl)propane in 100 ml of dry chloroform.Reflux (70° C.) was maintained for 20 hours. The viscous cloudy solutionwas poured into one liter of methanol in a Waring blender. Theprecipitate was collected by filtration. Residual tri-n-butyl tinchloride was removed by continuous extraction for 16 hours withmethanol.

The structure of the resulting "Bisphenol A" polycarbonate was confirmedby ¹³ C n.m.r. spectroscopy and infra-red spectrophotometry.

EXAMPLE 5

This example describes the preparation of a copolyester having therepeat units ##STR30##

A mixture of 3.52 grams (0.04 mol) of 1,4-but-2-enediol, 81.00 grams(0.36 mol) of 2,2'-bis(4-hydroxphenyl)propane, 256.86 grams (0.8 mol) oftributyltin methoxide and 600 ml of chlorobenzene were heated to refluxin a nitrogen atmosphere. Methanol was removed as the by-product using afractionating column. Upon completion, the mixture of stannylatedbisphenol and glycol was allowed to cool for 80° C.

To this solution was then added a mixture of 40.07 grams (0.2 mol) ofisophthaloyl dichloride and 40.07 grams (0.2 mol) of terephthaloyldichloride in 100 ml of dry chlorobenzene. The reaction mixture was thenrefluxed for 10 hours. The viscous cloudy solution was poured into twoliters of methanol in a Waring Blender and the precipitate collected byfiltration. Residual tri-n-butyl tin chloride was removed by continuousextraction for sixteen hours with methanol.

The structure of the polyester was confirmed by ¹³ C n.m.r spectroscopyand by infra-red spectrophotometry. The polymer had a reduced viscosityof 1.04 dl/g. (1% solution in chloroform).

EXAMPLE 6

This example describes preparation of the copolyester having the repeatunit ##STR31##

A mixture of 6.36 grams (0.028 mol) of 2,2'-bis(4-hydroxyphenyl)propane, 6.12 grams (0.032 mol) of4,4'dihydroxystilbene, 33.78 grams (0.06 mol) of bis-(tri-n-butyl tin)oxide and 150 ml of chlorobenzene were heated under reflux for twohours. A Dean-Stark trap was used to remove the water formed during thereaction. Thereafter 75 ml of the chlorobenzene was removed atatmospheric pressure. To this solution was then added 5.75 grams (0.03mol) of isophthaloyl dichloride in 25 ml dry chlorobenzene. After aperiod of not less than twenty minutes 5.75 grams (0.03 mol) ofterephthaloyl dichloride in 25 ml of dry chlorobenzene was added. Refluxwas maintained for 20 hours. The viscous cloudy solution was poured into250 ml of methanol in a Waring blender and the precipitate collected byfiltration Residual tri-n-butyl tin chloride was removed by continuousextraction for sixteen hours with methanol.

Infra-red data was consistent with the structure proposed. The polymerhad a reduced viscosity of 0.79 dl/g (1% solution in chloroform).

Copolyesters from "Bisphenol A" and3,3'-dichloro-4,4'-dihydroxystilbene, "Bisphenol A" and2,2',3,3'-tetramethyl-4,4'-dihydroxystilbene, and "Bisphenol A" and4,4-di(hydroxy)benzalazine were prepared in an analogous manner.

EXAMPLE 7 Preparation of the polythioester ##STR32## 4,4'-dithiol, 18.41grams (0.031 mol) of bis(tri-n-butyl tin)oxide and 150 ml of xylene wereheated under reflux in a nitrogen atmosphere for two hours. A Dean-Starktrap was used to remove the water formed during the reaction. Thereafter75 ml of the xylene was removed at atmospheric pressure and theremaining 75 ml at reduced pressure (20 mm H/g). After allowing theremaining 75 ml liquid to cool to room temperature 30 ml of drychloroform was added. To this solution was added 3.134 grams (0.015 mol)isophthaloyl dichloride in 25 ml of dry chloroform. After a period ofnot less than twenty minutes 3.134 grams (0.015 mol) of terephthaloyldichloride in 25 ml of dry chloroform was added. Reflux (70° C.) wasmaintained for 20 hours. The cloudy suspension was poured into 250 ml ofmethanol in a Waring blending and the precipitate collected byfiltration. Residual tri-n-butyl tin chloride was removed by continuousextraction for sixteen hours with methanol.

Infra-red spectrophotometric data was consistent with the structureproposed.

EXAMPLE 8 Preparation of the polyester ##STR33##

A mixture of 9.236 grams 0.084 mol) of hydroquinone, 50 grams (0.084mol) of bis(tri-n-butyl tin) three hours. A Dean-Stark trap was used toremove the water formed during the reaction. Thereafter 100 ml of thexylene was removed at atmospheric pressure and the remaining 100 ml atreduced pressure (20 mm/Hg). After allowing the remaining liquid to coolto room temperature 100 ml of dry chloroform was added. To this solutionwas then added 17.029 grams (0.084 mol) of terephthaloyl dichloride in50 ml of dry chloroform. Reflux (70° C.) was maintained for 20 hours.The resulting cloudy suspension was poured into 250 ml of methanol in aWaring blender and the precipitate collected by filtration.

Infra-red spectrophotometric data was consistent with the structureproposed.

EXAMPLE 9 Preparation of the polyphosphonic ester ##STR34##

A mixture of 49.42 grams (0.22 mol) of 2,2'-bis(4-hydroxyphenyl)propane,129.04 grams (0.22 mol) of bis(tri-n-butyl tin)oxide and 300 ml ofxylene were heated under reflux in a nitrogen atmosphere for 4 hours. ADean-Stark trap was used to remove the water formed during the reaction.Thereafter 200 ml of the xylene was removed at atmospheric pressure andthe remaining 100 ml under reduced pressure (20 ml H/g). After allowingthe remaining liquid to cool to room temperature 100 ml of drychloroform was added. To this solution was slowly added 42.89 grams(0.22 mol) of phenylphosphonic acid dichloride in 100 ml of drychloroform. Reflux (70° C.) was maintained for 20 hours. The clearviscous solution was poured into one liter of hexane in a Waring blenderand the precipitate collected by filtration.

Infra-red spectrophotometric data was consistent with the structureproposed. The polymer had a reduced viscosity of 0.55 dl/g. (1% solutionin chloroform).

EXAMPLE 10 Preparation of the polyester ##STR35##

A mixture of 14.90 grams (0.06 mol) ofbis(4-hydroxyphenyl)sulphone,35.49 grams (0.06 mol) of bis(tri-n-butyltin)oxide and 400 ml of xylene were heated under reflux for four hours.A Dean-Stark trap was used to remove the water formed in the reaction.Thereafter 200 ml of the xylene was removed at reduced pressure (20mm/Hg). After allowing the remaining liquid to cool to room temperature50 ml of dry chloroform was added. To this solution was slowly added16.49 grams (0.06 mol) of hexafluoroglutaroyl dichloride in 150 ml ofchloroform Reflux (70° C.) was maintained for 20 hours. The cloudysuspension was poured into 500 ml of methanol in a Waring blender andthe precipitate collected by filtration. Residual tri-n-butyl tinchloride was removed by continuous extraction for sixteen hours withhexane.

Infra-red spectrophotometric data was consistent with the structureproposed. ##STR36## was prepared by a similar method.

EXAMPLE 11 Preparation of the polyamide ##STR37##

A mixture of 16.88 grams (0.046 mol) of diethyl-aminotri-n-butylstannane, 5.79 grams (0.023 mol) of 4,4'-diaminodiphenylsulphone and 25ml of dry chlorobenzene were stirred at room temperature for 2 hours andthen refluxed for 1 hour during which time diethylamine was removed.After allowing the solution to cool to room temperature 4.74 grams(0.023 mol) of isophthaloyl dichloride in 25 ml of chlorobenzene wasadded. The reaction was then refluxed (70° C.) for 17 hours at 100° C.After cooling the reaction mixture was poured into methanol in a Waringblender and the precipitate collected by filtration. Residualtri-n-butyl tin chloride was removed be continuous extraction for 16hours with methanol.

¹³ C n.m.r. spectroscopic and infra-red spectrophotometric data wereconsistent with the proposed structure of the polyamide.

EXAMPLE 12

This example describes the preparation of the block copolyesteramidehaving blocks ##STR38##

Using the procedure outlined in Example 1 a polyester was prepared from30.75 grams (0.135 mol) of 2,2-bis(4-hydroxyphenyl)propane, 80.30 grams(0.135 mol) of bis(tri-n-butyl tin)oxide, 12.14 grams (0.06 mol) ofisophthaloyl dichloride and 12.17 grams (0.06 mol) of terephthaloyldichloride. An excess of the tin compound was used to ensure that theresulting polyester was terminated at each end with a tri-n-butyl tingroup.

Simultaneously but in a separate flask a polyamide was prepared using54.97 grams (0.219 mol) of N,N'-bis (trimethylsilyl)-m-phenylenediamineand 47.42 grams (0.23 mol) of isophthaloyl dichloride. An excess of thedichloride compound was used to ensure that the resulting polyamide wasterminated at each end with a chloride group. During the reactiontrimethyl chlorosilane by product was removed. Upon completion ofreaction a vacuum was applied (50 mm/Hg) to ensure removal of lasttraces of Me₃ SiCl.

The ester solution was then added to the amide solution. After theaddition was complete the chloroform was distilled out. The remainderwas heated to 70° C. for 20 hours. The resulting viscous cloudy mixturewas poured into one liter of methanol and the precipitate collected byfiltration. Residual tri-n-butyl tin chloride was removed by continuousextraction of the solid for 16 hours using methanol.

Infra-red spectrophotometric data was consistent with the proposedstructure Upon extraction with solvents for the respective homopolymersno change was observed in the infra-red spectrum of the copolymer.

EXAMPLE 13

Preparation of the polyester ##STR39##

A mixture of 32.48 grams (0.14 mol) of 2,2-bis(4-hydroxyphenyl)propane,91.37 (0.28 mol) grams of methoxytri-n-butyl tin and 400 ml of distilledchlorobenzene were heated to reflux Methanol was removed as theby-product, using a fractionating column. In all 9.10 ml of methanol wasremoved along with 150 ml of solvent over 4.5 hours. The solution ofstannylated 2,2-bis(4-hydroxyphenyl)propane was allowed to cool to 80°C. whereupon a solution of 14.44 (0.07 mol) grams of terephthaloyldichloride and 14.44 grams (0.07 mol) of isophthaloyl dichloride in 100ml of chlorobenzene was added over 1 minute. The reaction mixture wasbrought to reflux and maintained for 1 hour. Then sufficient solvent wasremoved from the reaction to maintain a reaction temperature of 140° C.This temperature was maintained for 10 hours After allowing to cool to80° C. the polymer was precipitated by pouring the viscous solution into1 liter of hexane in a Waring blender. The polymer was collected byfiltration and final traces of tri-n-butyl tin chloride by-productremoved by continuous extraction of the product with methanol for 8hours.

The structure of the polyester was confirmed by ¹³ C N.M.R. spectrocopyand by I.R. spectrophotometry. The RV in chloroform of a 0.5% solutionwas 0.87.

EXAMPLE 14 Preparation of the polyoxylate ##STR40##

A mixture of 49.50 grams (0.3296 mol) of triethylene glycol, 211.65 g(0.6592 mol) of tributyltin methoxide and 300 mls of dry chlorobenzenewere heated to reflux. Methanol was removed as the by-product using afractionating column. After all the methanol had been removed, a further75 mls of chlorobenzene was removed to ensure its complete removal. Thesolution of stannylated glycol was cooled to 0° C. and to this solutionwas added 41.84 grams (0.3296 mol) of oxalyol chloride in 100 mls ofchlorobenzene. The reaction was very exothermic. After the addition wascomplete the addition funnel was washed through with 3×10 mls ofchlorobenzene. The semi-viscous solution was left stirring at roomtemperature overnight.

The two layers were then separated and the product layer, the viscousone, was washed with 5×150 ml of diethylether. Residual ether was thenremoved under vacuum leaving a pale yellow highly viscous oil whichslowly solidified over 2 weeks.

The structure of the polymer was confirmed by 'H n.m.r. spectroscopy andinfra-red spectrophotometry

G.P.C. chromatographic analysis of the material gave it an Mn=7000polystyrene equivalents.

EXAMPLE 15 Preparation of the polysulphonate ester ##STR41##

A mixture of 28.41 grams (0.1244 mol) of 2,2'-bis (4-hydroxyphenyl)propane, 79.93 g (0.2489 mol) of tributyltin methoxide and 300 mls ofdry chlorobenzene were heated to reflux. Methanol was removed as theby-product using a fractionating column. After all the methanol had beenremoved a further 100 mls was removed to ensure its complete removal.The stannylated bisphenol was allowed to cool to 90° C. To this solutionwas then added 45.70 g (0.1245 mol) of diphenyl ether-4,4'-di(sulphonylchloride) in 100 mls of dry chlorobenzene. After refluxing for 10 hoursthe polymer was precipitated by pouring into methanol in a Waringblender. After filtration the tributyltin chloride residues wereextracted into diethyl ether.

The structure of the polymer was confirmed by 'H n.m.r. spectroscopy andinfra-red spectrophotometry.

The polymer had a reduced viscosity of 0.87 dl/g. solution inchloroform).

EXAMPLE 16 Preparation of the copolyester having the repeat units##STR42## A mixture of 23.40 grams (0.1025 mol) of 2,2'-bis(4-hydroxyphenyl) propane, 12.72 (0.1025 mol) of methyl hydroquinone,131.66 grams (0.410 mol) of tributyltin methoxide and 400 mls of drychlorobenzene were heated to reflux. Methanol was removed as theby-product using a fractionating column. After all the methanol had beenremoved a further 75 mls of chlorobenzene was removed to ensure itscomplete removal. The stannylated mixture of bisphenols was allowed tocool to 90° C. To this solution was then added a mixture containing20.81 grams (0.1025 mol) of isophthaloyl dichloride and 20.81 grams0.1025 mol) of terephthaloyl dichloride in 200 mls of chlorobenzene.After refluxing for 10 hours the viscous mass was poured into 1 liter ofmethanol. The precipitated polymer was transferred to a Waring blenderwith more methanol and broken up. The fiberous polymer was collected byfiltration and the tributyltin residues extruded into methanolovernight.

The structure of the polymer was confirmed by 'H n.m.r. spectroscopy andinfra-red spectrophotometry.

The polymer had a reduced viscosity of 1.83 dl/g (1% solution ino-chlorophenol.

EXAMPLE 17 Preparation of the polyester ##STR43##

A mixture of 9.06 grams (0.0397 mol), 19.80 g grams (0.0397 mol) ofthallous ethoxide and 50 ml of dry chlorobenzene was brought up toreflux. Ethanol was removed as the by-product using a fractionatingcolumn. After all the ethanol had been removed a further 10 mls ofchlorobenzene was removed to ensure its complete removal. The thallousbisphenate was allowed to cool to 80° C. To the cooled mixture was addeda mixture of 4.03 grams (0.0198 mol) of iso-phthaloyl dichloride and4.03 grams (0.0198 mol) of terephthaloyl dichloride in 150 mls of drychlorobenzene. After refluxing for 10 hours the white mass was pouredinto methanol. The polymer was extracted from the thallous chlorideby-product by dissolving the polymer in chloroform, filtering andre-precipitating in methanol.

The structure of the polyester was confirmed by 'H n.m.r. spectroscopyand infra-red spectrophotrometry.

The polymer had a reduced viscosity of 0.46 dl/g. (1% solution inchloroform).

EXAMPLE 18 Preparation of the polyester having the repeat units##STR44##

A mixture of 8.21 grams (0.066 mol) of methylhydroquinone, 10.93 grams(0.016 mol) of Teracol 650 (tradename from Du Pont), 53.00 grams (0.165mol) of tributyltin methoxide and 150 mls of dry chlorobenzene wereheated to reflux. Methanol was removed as the by-product using afractionating column. After all the methanol had been removed a further25 mls of chlorobenzene was removed to ensure its complete removal. Thestannylated mixture was then allowed to cool to room temperature. To thecold solution was then added 16.58 grams (0.082 mol) of terephthaloyldichloride in 75 mls of dry chlorobenzene. After refluxing for 10 hours,2 ml of benzoyl chloride was added to end cap the polymer. After 2 hoursthe cloudy viscous mass was poured into 250 mls of methanol in a Waringblender and the polymeric precipitate collected by filtration. The tinresidues were extracted in methanol overnight.

The structure of the polymer was confirmed by 'H n.m.r. spectroscopy andinfra-red spectrophotometry.

The polymer had a reduced viscosity of 0.60 dl/g (1% solution ino-chlorophenol).

A similar material was prepared from 2,2'-bis(4-hydroxyphenyl) propane,HO(CH₂ CH₂ CH₂ CH₂ O)₉ H (Teracol 650, tradename from du Pont),tributyltin methoxide, isophthaloyl dichloride and terephthaloyldichloride, having a reduced viscosity of 0.83 dl/g. (1% solution inchloroform).

EXAMPLE 19 Preparation of the co-polyester siloxane ##STR45##

A mixture of 38.75 grams (0.1697 of (2,2'-bis-(4-hydroxyphenyl) propane,109.00 grams (0.3395 mol) of tributyltin methoxide and 300 mls of drychlorobenzene were heated to reflux. Methanol was removed as theby-product using a fractionating column. After all the methanol had beenremoved a further 100 mls of chlorobenzene was removed to ensure itscomplete removal. The stannylated bisphenol was allowed to cool to 90°C. To this solution was then added a mixture of 12.14 grams (0.0598 mol)of isophthaloyl dichloride and 12.14 g (0.0598 mol) of terephthaloyldichloride in 100 mls of dry chlorobenzene. After half an hour at 90° C.a solution of 13.89 grams (0.0501 mol) of 1,5-dichlorohexamethyltrisiloxane was added in 50 mls of dry chlorobenzene. After refluxingfor 10 hours the viscous mass was allowed to cool and then poured intocold (0° C.) methanol and the material broken up in a Waring blender.The fiberous polymer was collected by filtration and the tributyltinchloride residues extracted into diethyl ether overnight.

The structure of the polymer was confirmed by 'H n.m.r. spectroscopy andinfra-red spectrophotometry.

The polymer had a reduced viscosity of 0.65 dl/g. (1% solution inchloroform).

EXAMPLE 20 Preparation of the polyester ##STR46##

30.06 grams (0.0848 mol) of 2,2'-bis (4-hydroxyphenyl) propane and 54.46grams (0.1696 mol) of tributyl tin methoxide were reacted together in300 mls of dry chlorobenzene according to Example 13. To the stannylatedbisphenol solution was then added a mixture of 15.03 g (0.0424 mol) ofbis(phenylthio)isophthalate and 15.03 grams (0.0424 mol) ofbis-(phenylthio) terephthalate in 100 mls of chlorobenzene. Afterrefluxing for 15 hours the polymer was precipitated by pouring intomethanol in a Waring blender. After filtration the tributyltinthiophenol residues were removed by extraction into methanol.

The structure of the polymer was confirmed by 'H n.m.r. spectroscopy andinfra-red spectrophotometry.

The polymer had a reduced viscosity of 0.80 dl/g. (1% solution inchloroform).

EXAMPLE 21 Preparation of the polyester ##STR47##

A mixture of 8.05 grams (0.0353 mol) of 2,2'-bis-(4-hydroxyphenyl)propane, 25.25 grams (0.0353 mol) of bis-triphenyltin oxide and 200 mlsof dry chlorobenzene were heated to reflux. The water of reaction wasremoved using a Dean-Stark head. After all the water had been removedthe solution was allowed to cool to 90° C. To this solution was added amixture of 3.57 grams (0.0176 mol) of isophthaloyl dichloride and 3.57grams (0.0176 mol) of terephthaloyl dichloride in 50 mls of drychlorobenzene. After refluxing for 10 hours the polymer was precipitatedinto methanol in a Waring blender. The fiberous polymer was collected byfiltration and triphenyltin chloride residues removed by extracting intomethanol.

The polymer had a reduced viscosity of 0.63 dl/g. (1% solution inchloroform).

EXAMPLE 22 Preparation of the polyester ##STR48##

A mixture of 7.636 grams (0.03345 mol) of 2,2'-bis (4-hydroxyphenyl)propane, 8.410 grams (0.03345 mol) of bis (trimethylgermanium) oxide and70 mls of dry chlorobenzene were heated to reflux in a nitrogenatmosphere for 4 hours. A Dean Stark trap was used to remove the waterformed during the reaction. After all the water has been collected thereaction mixture was allowed to cool to 90° C. After cooling a 1:1mixture of 6.791 grams (0.03345 mol) of isophthaloyl and terephthaloyldichlorides in 20 mls of dry chlorobenzene was rapidly added. Thereaction mixture was then refluxed for 30 hour and trimethylgermaniumchloride removed as it was formed. After 30 hours the reactionmixture was colorless and had achieved maximum viscosity. The polyesterwas precipitated by pouring the reaction mixture into methanol in aWaring blender. The fiberous polymer was collected by filtration andresidual trimethyl germanium chloride removed by washing with methanol.

'H n.m.r spectroscopy and infra-red spectrophotometry were consistentwith the expected structure.

The polyester had an Rv=0.46 dl/g (1% solution in chloroform).

EXAMPLE 23 Preparation of the polyester ##STR49##

To a suspension of 12.89 grams (mol) of 2,2'-bis(4-hydroxyphenyl)propane in of dry chloroform at room temperature was added a 15.64 grams(0.0565 mol) of 1,1'-dimethylstannocene in 50 mls of dry chloroform.After stirring at room temperature for 2 hours a solution of 11.47 grams(0.0565 mol) of a 1:1 mixture of isophthaloyl and terephthaloyldichlorides in 50 mls of dry chloroform was added. The resultant mixturewas stirred at room temperature for 10 hours and then heated to refluxfor 4 hours. After cooling the viscous cloudy mixture was poured intoone liter of methanol to precipitate the polymer. Co-precipitatedstannous methoxide was removed by re-dissolving the polymer inchloroform, filtering and re-precipitating in methanol.

The 'H n.m.r. and the infra-red spectra of the material were consistentwith the proposed structure.

The polymer had a reduced viscosity of 0.41 dl/g. (0.5% solution inchloroform).

EXAMPLE 24 Preparation of the polyester ##STR50##

To a solution of 4.88 grams (0.0786 mol) of ethylene glycol in 100 mlsof dry chlorobenzene was added 50.47 grams (0.1572 mol) of tributyltinmethoxide. The mixture was then heated to boiling and the methanolremoved via a fractionating column. After all the methanol and 20 ml ofchlorobenzene had been removed the mixture was allowed to cool to roomtemperature. To the cold solution was then added 41.62 grams (0.1572mol) of hexachloroacetone and the resultant mixture stirred at roomtemperature for 1 hour. After this time a solution of 15.96 grams(0.1572 mol) of a 1:1 mixture of isophthaloyl and terephthaloyldichlorides in 50 mls of chlorobenzene were added and the whole mixturestirred at room temperature for 4 hours and then heated to reflux for 4hours. The polymerisation was terminated by pouring the mixture intomethanol whereupon the polymer precipitated. After filtering off theby-product residual tributyltin chloride was removed by extracting withmethanol.

The 1 H, n.m.r., ¹³ C n.m.r. and infra-red spectra were consistent withthe proposed structure.

We claim:
 1. A method of preparing a thioester, thiocarbonate,thioamide, or thioimide polymer or copolymer, comprising reacting amonomeric, oligomeric, or polymeric nucleophilic reactant of the formula##STR51## where E is

    (R').sub.b M

or ##STR52## each M is independently tin, germanium, lead, or thallium;each R' is independently a substituted or unsubstituted alkyl or arylgroup; each Y is independently oxygen, sulfur, or substituted nitrogenor phosphorus; each A¹ is independently an aromatic, aliphatic,aromatic/aliphatic, heterocyclic, alicyclic, siloxyl, or silanemonomeric, oligomeric or polymeric moiety; each a is an integer two lessthan the valence of the element M to which it pertains; each b is aninteger one less than the valence of the element M to which it pertains;and x and y are each independently an integer greater than or equal to1; with a substantially stoichiometric amount of an electrophilicreactant selected from the group consisting of (i) a compound of theformula ##STR53## where each X is independently halide, imidazole, RO-,RS-, or a group capable of reacting with the first reactant to eliminatea by-product containing M and X, R being a substituted or unsubstitutedaromatic or aliphatic group or hydrogen; each B is independently carbon,phosphorous, sulfur, silicon, or a direct bond; each Z is independentlyoxygen, sulfur, or an imino group; each D is independently an aromatic,aliphatic, RO-, RS-, or R₂ N- group is B is silicon; each d isindependently 1 if B is carbon; 0 or 1 if B is phosphorus; 0, 1, or 2 ifB is sulfur; and 0 is B is silicon or a direct bond; each e isindependently 0 if B is carbon, sulfur, or a direct bond; 1 if B isphosphorus; and 2 if B is silicon; and A² is an aromatic, aliphatic,aromatic/aliphatic heterocyclic, alicyclic, siloxyl, or silanemonomeric, oligomeric, or polymeric moiety, which is the same ordifferent from A¹, or a direct bond; (ii) a compound of the formula##STR54## (iii) combination of (i) and (ii); with the proviso that atleast one Y and/or Z is sulfur; to produce a polymer having the repeatunit ##STR55## where A³ is A² or Y-A¹ -Y.
 2. A method according to claim1 wherein M is tin.
 3. A method according to claim 1 or 2 wherein E is##STR56##
 4. A method according to claim 1 or 2 wherein A¹ is a siloxylor silane monomeric, oligomeric, or polymeric moiety.
 5. A methodaccording to claim 1 or 2 wherein A² is a siloxyl or silane monomeric,oligomeric, or polymeric moiety.
 6. A method according to claim 1 or 2wherein B is sulfur, Z is oxygen, and d is
 2. 7. A method according toclaim 1 or 2 wherein B is phosphorus.
 8. A method according to claim 1or 2 wherein B is silicon
 9. A method according to claim 1 wherein M isgermanium.
 10. A method according to claim 1 wherein M is lead.
 11. Amethod according to claim 1 wherein M is thallium.
 12. A methodaccording to claim 1 wherein Y is oxygen.
 13. A method according toclaim 1 wherein Y is NR², where R² is lower alkyl or hydrogen.
 14. Amethod according to claim 1 wherein A¹ is substituted or unsubstitutedp-phenylene, m-phenylene, 1,4-napthlene, 2,6-naphthylene,2,6-pyridinediyl, 2,6-pyridinediyl, C-1 through C-6 saturated orunsaturated alkylene, or

    -p-Ph-K-p-Ph-

where p-Ph is p-phenylene and K is a direct bond, O, S, carbonyl,sulfone, or C-1 through C-6 saturated, unsaturated, or fluorinatedalkylene.
 15. A method according to claim 1 wherein A¹ is p-phenylene,m-phenylene, or

    -p-Ph-K-p-Ph-

where K is sulfone, methylene, or isopropylidene.
 16. A method accordingto claim 1 wherein A² is substituted or unsubstituted p-phenylene,m-phenylene, 1,4-napthylene, 2,6-naphthylene, 2,6-pyridinediyl,2,6-pyridinediyl, C-1 through C-6 saturated, unsaturated, or fluorinatedalkylene, or a direct bond, or

    -p-Ph-K-p-Ph-

where p-Ph is p-phenylene and K is a direct bond, O, S, carbonyl,sulfone, or C-1 through C-6 saturated, unsaturated, or fluorinatedalkylene.
 17. A method according to claim 1 wherein A² is p-phenylene,m-phenylene, or

    -p-Ph-K-p-Ph-

where K is sulfone, methylene, or isopropylidene.
 18. A method accordingto claim 1 wherein A¹ and A² are independently selected from the groupconsisting of p-phenylene, m-phenylene, and

    -p-Ph-K-p-Ph-

where K is sulfone, methylene, or isopropylidene.